Treatment of textiles and composition therefor



Patented Jan. 4, 1949 TREATMENT OF TEXTILES AND COM- POSITION THEREFORHenry L. Van Mater, Highland Park, N. J., as-

signor, by mesne assignments, to National Lead Company, New York, N. Y.,a corporation of New Jersey No Drawing. Application September 20, 1944,Serial No. 555,044

Claims. 1

The present invention relates to compositions for rendering textilematerials water repellent, to water repellent textile materials and tomethods of treating textile materials with such compositions. Theinvention has particular reference to the employment of zirconiumcompounds for this purpose.

Suggestions have been made heretofore for rendering textile. materialswater repellant by employing zirconium compounds as the textile treatingagent and, in general, the textile was impregnated with a basiczirconium compound such as the hydrate upon which a soap forming fattyacid was deposited. Such an operation normally required more than onebath and, hence, there was no control of the relative amounts ofmaterials used and, furthermore, where zirconium salts of mineral acidswere employed as the starting materials, tendering of the cloth byreason of the high acid content of such salt solutions was usuallyencountered. In general, such prior treatments are defective in that thecloth was not permanently treated since the precipitated fatty acid wasremoved by emulsification when washed in soap solutions as inlaundering, and by extraction when cleaned with the ordinary drycleaning solvents.

It is an object of the present invention to pro- I vide a bathcomposition for treating textile goods, which bath contains controlledand critical amounts of materials.

It is also an object of the invention to provide a textile treatingmethod wherein compounds of zirconium that are relatively inert to drycleaning solvents and to soap solutions are placed upon textile goods incontrolled and desired amounts.

It is a further object of the invention to use relatively non-acidiczirconium compounds for the treatment of textile fibers.

It is also an object of the invention to provide textile treating bathsthat are relatively stable at ordinary temperatures but which possess arelatively well-defined decomposition point at and above which waterrepellant zirconium compounds are precipitated on and in the fiber to betreated.

In accordance with the present invention, a solution of the desiredconcentration oi zirconium salt is made by employing substantially anywater soluble zirconium compound. In general, zirconium salts of mineralacids are employed for this purpose. The zirconium salt is then changedto a water soluble double carbonate-by reacting the zirconium salt witha carbonate of and the like.

an alkali metal including ammonium. The resultant solution is mildlyalkaline and at room temperatures, and temperatures below about 0.,maybe maintained for considerable periods of time with but littledecomposition due to loss of carbon dioxide. However, at temperaturesabove about 0., decomposition of the double carbonate proceeds rapidlyand is complete in a matter of a few minutes. The amount of alkali metalcarbonate admixed with the soluble zirconium salt is substantially thatquantity necessary to produce the double carbonate in accordance withthe following reaction wherein zirconium sulfate and ammonium carbonateare the reactants:

The treating composition of the present inven-' tion is made by mixingwith the double carbonate an amount of soluble soap sufiicient to reactwith the double carbonate to produce a zirconium mono fatty acidcompound. The soluble soap may be substantially any soluble salt of anyof the soap forming higher fatty acids as, for instance, the alkali'metal salts including ammonium of oleic acid, stearic acid, palmiticacid, The resultant solution is a colloidal solution of the doublecarbonate and soap which may be maintained at room temperatures forseveral hours without appreciable chemical action 'occuring between theingredients.

However, when the temperature of the bath is raised, the speed of thereaction is rapidly accelerated and, above about 60 0., carbon dioxideis evolved copiously, and reactionoccurs between the resulting zirconylion and the soap to form a basic zirconyl mono fatty acid, a compoundinsoluble in water and in most organic solvents, particularly those usedas dry cleaning solvents. At temperatures at which decomposition occurs,the double carbonate reacts with the soluble salt of the fatty acid inaccordance with the following equation where F" represents a fatty acidradical:

It will be noted that all soluble products are either decomposed andremoved by heating or it not so decomposed and removed are then removedin the final washing. Thus the insoluble basic zirconyl mono fatty acidcompound remains deposited in or on the material so treated.

In accordance with the present invention, therefore, the material to berendered water repellant is impregnated or padded with the colloidalmixture of soap and soluble double carbonate of zirconium at atemperature below the rapid decomposition point of the mixture. Thematerial, such as textile goods, may be impregnated or padded in anysuitable manner although, in general, the goods will be immersed in thesolution and excess solution removed by squeezing or centrifuging sothat the goods re-' tain sufllcient solution to produce water repellencyupon subsequent processing. Thereafter, the impregnated goods are heatedin any desirable fashion to a temperature above which rapiddecomposition occurs with the formation of zirconyl mono fatty acid.This may be done by treating the goods on hot or calender rolls or bycontact with hot air. Thereafter, the goods, having deposited thereon,or having absorbed therein, the precipitated zirconyl mono fatty acidare washed to eliminate soluble by-products and are finally dried andfinished in any desirable fashion.

In carrying out the method, certain operating controls must be followed;namely, the impregnation should be carried out below about 50 C. and thegoods impregnated with the treating solution should be then heated to atemperature above about 60 C. and preferably to 80 to 100 0.Furthermore, the amount of soluble fatty acid soap employed should berelatively close to one mole of fatty acid soap for each mole ofzirconium salt present. If more than one mole of fatty acid salt isused, a precipitate is obtained which is zirconyl mono fatty acidcombined with a mole of free fatty acid, which type of compound is notentirely insoluble in dry cleaning solvents as the free fatty acid isextractable from the complex. Where the mole relation is such thatsubstantially less than one mole of fatty acid soap is employed per moleof zirconium salt, the fullest advantages of the present invention arenot obtained.

Somewhat better control of the operating procedure is obtained if careis taken with respect to the type or lay-product salts produced, itbeing preferred that such salts be of the type which readily formsupersaturated solutions. Sodium acetate and sodium sulfate are salts ofthis type. By-product salts, as for instance sodium chloride. show sometendency to precipitate the colloidal mixture by salting out thecolloid. In such in-- stances it is advantageous to add an equal moleratio of ammonium acetate. There is thus formed. from the soluble soap,an ammonium fatty acid and acetate of alkali metal.

The following illustrations will serve to show the application of themethod. The concentrations of chemicals are merely by way ofillustration since the concentration will depend upon the over-alloperating conditions and the type of goods being treated. It will beunderstood, however, that the manipulative steps of the treatment aresubstantially the same under all conditions.

- Example N0. 1

56.8 grams of ammonium carbonate are dissolved in 500 ml. of water atroom temperature. To the resulting solution is added 40 grams ofzirconium sulfate crystals with mechanical stirring. Stirring iscontinued until the zirconium sulfate is dissolved.

34% grams of sodium oleate are dissolved in 500 ml. of water withheating to approximately 4 C. The soap solution is then cooled tobetween 40 and 50 C. when it is then mixed with the solution containingthe zirconium double car bonate.

The material to be made water repellant is then introduced into thecolloidal mixturefor a period of 30 to 60 seconds. It is then freed fromexcess solution by squeezing or centrifuging andheated either in hotair, to between 80 C. and C., or by hot calendering. The material isthen passed into water to dissolve out b'y-product salts, and finallydried.

. Example No. 2

Example No. 3

30 grams of ammonium carbonate are dissolved in a solution made up of425 ml. of water .and '75 ml. of 5 Normal ammonium hydroxide. 30 grams Iof zirconium sulfate crystals are added to the above solution withstirring. Stirring is continued until solution is complete.

24 grams of stearic acid are added to 325 ml. of water and 1'75 ml. of 5Normal ammonium hydroxide. The mixture is heated until the resultingsolution is clear. The solution is then cooled to between 40 and 50 C.and then mixed with the zirconium solution.

The promdure for treatment of the material is the same as in Example 1.

Example No. 4

1%.10 grams of anhydrous sodium carbonate are dissolved in 250 ml. ofwater. 36.25 grams of zirconium oxychloride are dissolved in 250 m1. ofwater. The solution containing the zirconium is introduced into thesodium carbonate solution resulting in the precipitation of zirconiumcarbonate. The precipitate is washed and filtered and to the paste isadded 22.15 grams of anhydrous sodium carbonate. This producesresolution of the precipitate to form the double salt of zirconiumsodium carbonate. This solution is made up to 500 ml. volume.

34.5 grams of sodium stearate are dissolved in 500 ml. of water withheating and then cooled to between 40 and 50 C. This solution is thenmixed with the zirconium solution. 40.9 grams of ammonium acetate isthen dissolved in the above colloidal mixture.

The procedure for the treatment of the material to be rendered waterrepellant is the same as in Example 1.

Example No. 5

ing precipitation of the zirconium. The precipitate is washed andfiltered. To the paste is added 25% grams of ammonium carbonate whichcauses resolution of the precipitate. This solution is made up to 500ml. volume.

34.2 grams of sodium oleate is dissolved in 500 ml. of hot water whichis then cooled to between 40 and 50 C. The soap solution is then addedto the zirconium solution. The procedure for the treatment of thematerial to be rendered water repellant is the same as in Example 1.

The amount of water repellant material added to the goods will dependupon several factors, viz., the type ofgoods being treated, whetherlight or heavy, whether tight or loosely woven, whether cotton, woolenor mixed goods, the set of the squeeze rolls, etc. In normal operationthe goods contain sufhcient material to produce the desired waterrepellency when finished. Although illustrative concentrations oftreating chemicals are given herein, it will be understood thatvariations may be made therefrom without departing from the scope orspirit of the invention.

The term alkali metal as used in the claims designates the alkali metalsand ammonium.

What is claimed is:

1. The method of rendering textile goods water repellant which comprisesimpregnating the goods with a solution of a soluble double carbonate ofzirconium and a soluble soap in amounts to react to form a zirconyl monofatty acid compound at a temperature below which reaction occurs andthereafter elevating the temperature of the so impregnated goods above60 C. so that reaction occurs with precipitation of zirconyl mono fattyacid compound.

2. The method of rendering textile goods water I 3. The method ofrendering cellulosic fiber material water repellent which comprisesimpregnating such material with a solution of a soluble alkaline doublecarbonate of ammonium and zirconium, and soap as reactants at atemperature below 'C. and thereafter elevating the temperature of the soimpregnated material above C. to induce reaction with precipitation ofzirconyl mono fatty acid compound rendering said material waterrepellant.

4. A waterproofing composition which comprises an alkaline aqueoussolution of a soluble soap, and a soluble double carbonate of azirconium salt and an alkali metal carbonate, the soap and zirconiumsalt being present in amounts sufficient to form a zirconyl mono fattyacid compound.

5. A waterproofing composition which comprises an alkaline aqueoussolution of a soluble soap, and a soluble double carbonate of azirconium salt and ammonium carbonate, the soap and zirconium salt beingpresent in amounts sufficient to form a zirconyl mono fatty acidcompound.

HENRY L. VAN MATER.

REFERENCES CITED The following references'are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,536,254 White May 5, 19252,191,982 Doser et a1. Feb. 27, 1940 2,221,975 Kinzie Nov. 19, 19402,252,658 Bigelow Aug. 12, 1941 2,289,316 Myers July '7, 1942 2,328,431Doser et al Aug. 31, 1943

